ES2485907T3 - Moisturizer and dispersant, production and use thereof - Google Patents

Abstract

Addition compounds and their salts, characterized in that the addition compounds can be obtained by reacting (a) one or more polyisocyanates with at least two isocyanate groups per molecule with (b1) one or more compounds of the formula (Ia) Y- XH (Ia) where XH represents a group reactive against isocyanates and Y represents a polymeric monomer group, non-reactive against isocyanates, without tertiary amino groups, which comprises one or more aliphatic, cycloaliphatic and / or aromatic groups, where the compound of the general formula (Ia) has an average molecular mass in number Mn less than 20,000 g / mol and where at least 55% molar of the compounds of the formula (Ia) have an average molecular weight in number Mn of 150 to 10,000 g / mol and which represent XH-functionalized poly (alkylene oxides) whose content of alkylene oxide units with at least three carbon atoms is 40 to 100 mole% with respect to the total content of units of alkylene oxide, with the proviso that 20% to 90% of the isocyanate groups of component (a) react with the compounds of the formula (Ia), (b2) one or more compounds of the formula (Ib) G- ( XH) n (Ib) where XH represents an isocyanate reactive group and n represents 2 to 4, and G represents an aliphatic, cycloaliphatic and / or aromatic containing at least 2 carbon atoms, without tertiary amino groups, with average molecular weight in maximum Mn number of 3000, in an amount such that 0 to 60% of the isocyanate groups of the polyisocyanate originally used react, with the proviso that by reactions (b1) and (b2) in total they react at least 20% and maximum 90% of the isocyanate groups originally used, (c1) one or more compounds of the general formula (IIa) ZQ (IIa) where Q represents -NH2, -NHR or OH, where R represents a linear or branched alkyl group with 1 to 18 carbon atoms, and Z represents a basic organic residue with at least one tertiary amino group that does not contain reactive groups against isocyanate, and (c2) optionally one or more compounds of the general formula (IIb)

Description

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

E09711814

07-28-2014

DESCRIPTION

Moisturizer and dispersant, production and use thereof.

The present invention relates to addition compounds and salts thereof suitable as humectants, dispersants and as dispersion stabilizers. The invention further relates to methods for preparing these addition compounds, for use as humectants and dispersants and dispersion stabilizers for organic and inorganic pigments, as well as fillers in organic and aqueous systems and solid materials in the form of powder or fiber capable of being incorporated into liquid systems, which are coated with such humectants and dispersants.

The humectants, dissolved or dispersed in a liquid, decrease the surface tension or interfacial tension and thereby increase the wettability of the solution. Dispersants are generally suitable for stabilizing solid particles in binders, lacquers, pigment pastes, plastics and plastic mixtures, for reducing the viscosity of such systems as well as for improving flow properties. Dispersion stabilizers are generally suitable for stabilizing already generated dispersions.

In order to incorporate solids into liquid media, high mechanical forces are required. It is usual to use dispersants in order to reduce the dispersion forces and to minimize the total energy input needed to deflocculate the solid particles and with this also minimize the dispersion time. Dispersants of this type are surfactant substances of anionic, cationic or neutral structure. These substances are applied in small quantities either directly to the solid or added to the dispersion medium. Furthermore, it is known that even after completely deflocculating solid agglomerates into primary particles, after the dispersion process, reaglomerations can be reached, whereby the dispersion effort is totally or partially canceled. As a result of inadequate dispersion and / or as a result of the reaglomeration, unwanted effects are generated such as an increase in viscosity in liquid systems, a deviation in color tone and a loss of gloss in lacquers and coatings, and a reduction in Mechanical resistance in plastics.

Today, quantities of different substances are used as dispersants for pigments and fillers. In addition to simple compounds with low molecular weight, such as, for example, lecithin, fatty acids and their salts and ethoxylated alkylphenol, for example, complex structures are also used as dispersants. Such structures especially include amino-functional and amido-functional systems, which find wide use within dispersants. In EP 158 406 and EP 208 041, for example, polyamine and amido-functional poly-oligocopolymers based on polyamines and polycaprolactones are used to disperse pigments, in which all reactive amino groups have been converted into amido groups. These products, however, represent complex reaction mixtures with low reproducibility and have poor solvent solubilities and inadequate compatibilities with binders and other resins.

At present, good results can already be obtained with polymeric dispersants based on polyisocyanates, as described, for example, in EP 0 154 678 A1 or EP 0 318 999 A2.

EP 0154 678 A1 describes dispersants that are obtained by adding monohydroxy compounds to polyisocyanates. The monohydroxy compounds contain at least one aliphatic, cycloaliphatic or aromatic group with at least one -O- and / or -COO- group. Preferred monohydroxy compounds are polyesters. Mainly, polyesters of aliphatic lactones and aliphatic monoalcohols are used. As another compound for the addition to polyisocyanates, di-or trifunctional polyethylene glycols are preferably used.

In EP 0 318 999 A2 the known addition compounds were modified from EP 0 154 678 A1 by additionally incorporating groups containing silicone and / or urethane. Dispersants obtained in this way have more universal compatibility.

WO 2006/132910 A2 describes polyurethane-based dispersants that are structured with a linear polyurethane main chain with various possible side chains. The compounds are characterized in that they contain at least one or preferably several reactive carbon-carbon double bonds per molecule. In this way, the compounds can be crosslinked after the dispersion operation either by Michael's addition of polyamines, or by free radical reaction.

From EP 0 335 197 A1 polyisocyanate polyaddition compounds are known which act as dispersants. For its preparation, polyesters or mainly polyethylene oxides are used, among others.

EP 0 731 148 A2 discloses the use of polyisocyanate addition products which have hydrophilic polyether chains, as suitable dispersants by incorporating solid substances as aqueous coating agents. Dispersants are prepared from the conversion of 5-100% equivalent (with respect to

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

E09711814

07-28-2014

isocyanate groups of the isocyanate component) of a monohydric alcohol component (B) as well as optionally other three optional components with a polyisocyanate. The monohydric alcohol component (B) is composed of at least one polyether monohydric alcohol with an ethylene oxide unit content of 50 to 99.5% by weight which can be modified by the addition reaction of epsilon-caprolactone in a amount of up to 40 by weight with respect to the weight of the monohydric alcohol.

In EP 0 826 753 A1 dispersants comparable to those of EP 0 731 148 A2 are produced in a solvent-free manner. With the difference that in this case only 0 to 75% equivalent of the mono-functional polyether component (B) based on ethylene oxide and optionally modified with epsilon-caprolactone are used. In addition, three other optional components can be reacted with the isocyanate component. The polymers disclosed in EP 0 827 973 A1 of the pigment formulation also contain high fractions of ethylene oxide in the polyalkylene oxide part.

WO 1997/26984 A1 describes reaction products of polyisocyanates with a Y-R-X component. In the YRX component, the X group with hydroxyl or amino function is linked to the nitrogen heterocycle through the R bridge such that a nitrogen atom of the heterocycle forms a tertiary amine with the R bridge. By the addition of the YRX tertiary amine to polyisocyanates, dispersants are obtained which are used in compositions with high solids content.

Special dispersants are disclosed in US 2004/0242727 A1 that can cure with radiation for the preparation of adhesive-free inks and coatings. These are the reaction products of polyisocyanates with at least one component that can be cured by radiation, preferably with (meth) acrylates, mainly polycaprolactonacrylates, and one or several other components.

US 2004/0260013 A1 discloses dispersants with acidic groups that are composed of a linear polyurethane backbone from low molecular weight diisocyanates, with side chains of C2-C4 poly-alkylene oxides. The alkylene oxide side chains must in this case be composed of at least up to 60, preferably up to 70 or even up to 80% by weight, based on the total weight of the alkylene oxides, of oxide units of ethylene.

DE 101 59 315 A1 describes dispersants from diisocyanates which contain an alkyl capped oligoalkylene oxide residue. The oligoalkylene oxide residue necessarily comprises one or more ethylene oxide groups and may also contain another branched alkyl residue, which however is not preferred.

WO 2004/104064 A2 treats a dispersant from diisocyanates with low molecular weight for non-aqueous systems which is structured from a linear polyurethane backbone with polyester, polyether and / or polyacrylate side chains.

The dispersants presented previously nevertheless often represent only partial solutions to the problems described at the beginning. Many of these products represent very complex and poorly defined reaction mixtures due to the many possible side reactions, which result in very limited compatibilities and poor solubilities. Therefore, these reactions can be carried out only in strongly diluted solutions and the final products have very low solids content, usually below 50% and in many cases even only 20-30%. The large amounts of solvent that are introduced through these products lead, however, to considerable problems in modern coating systems since as a consequence of the progressive efforts to produce environmentally compatible systems there is a need to decrease the amount of solvent as soon as possible (for example, in pigment concentrates, highly solid and ultra-highly solid paints) or even dispense completely with organic solvents. Products that contain polyester residues based on hydroxycarboxylic acids or their brass, such as epsilon-caprolactone and / or delta-valerolactone, are problematic due to their tendency to crystallization and present problems with poor solubility and compatibility. Mainly in the case of decorative paints based on aromatic-free test oaks, prior art dispersants may not be used or used only in a restricted manner.

Due to the large amount of organic and inorganic pigments and fillers used today, adequate stabilization of the solid particles to be dispersed by stable occupation in the face of surface desorption is not sufficiently guaranteed. Consequently, there are cases of agglomeration since the necessary efficient steric protection is lacking.

Due to the high application amounts of dispersants of this type with respect to the solids that must be dispersed (in the case of carbon black up to 100% dispersant with respect to the pigment), adhesion between the coatings is often worsened in the finished paint layer. layers and resistances, mainly water resistance, solvent resistance and scratch resistance.

10

fifteen

twenty

25

30

35

40

Four. Five

E09711814

07-28-2014

Therefore, the present invention is based on the objective of eliminating the previously described disadvantages of known dispersants, that is to say developing additives that at the same time effectively stabilize pigments or fillers, reduce the viscosity of the molten material of the paints. , plastic pastes or formulations to such an extent that processing with a high degree of loading is possible, without detriment of the strength properties in cured paints. Simultaneously, especially in the case of pigment pastes and pastes of fillers, broad compatibility has to be ensured so that they can be used in many different binders and coating materials. Furthermore, it is required that the dispersion additives used in accordance with the invention allow miscibility with each other of the flocculation-free pastes, or of the binders produced with these pastes.

In addition, dispersion additives must be provided such that they also act as humectants. Finally, the additives provided must also act as dispersion stabilizers, primarily as emulsion stabilizers.

On the other hand, the addition compounds provided in accordance with the invention must solve the problems associated with the incorporation of lactones to the dispersants of the prior art. As described above, high lactone fractions, mainly caprolactone, frequently lead to partially crystalline compounds with a high viscosity, which has a disadvantageous effect on processing properties, especially in the case of pigment paste production. and of cargo materials. Such lactone-based dispersants also possess the solubility problems previously described. Similar disadvantages are also known for dispersants that contain high polyethylene oxide fractions.

In addition, these addition compounds are of surprisingly wide utility, both in polar and non-polar binder systems. These greatly reduce the viscosity of the ground material during dispersion and therefore allow formulations with high solids content.

Surprisingly, it has been shown that a marked improvement in resistance properties can be achieved by dispersing and stabilizing the pigments or filler particles in binders, pigment pastes or plastic formulations if the addition compounds according to the invention are used, described below.

The objective is achieved by providing addition compounds and salts thereof that can be obtained by the reaction of

(a) one or more polyisocyanates with at least two isocyanate groups per molecule with

(b1) one or more compounds of the formula (la)

Y-XH (Ia)

where

XH represents a reactive group against isocyanates and Y represents a monomeric or polymeric group that is not reactive against isocyanates, without tertiary amino groups, which comprises one or more aliphatic, cycloaliphatic and / or aromatic groups, in which case the compound of the general formula (Ia) has an average molar mass in number Mn less than 20,000 g / mol and in which case at least 55% molar of the compounds of formula (Ia) have an average molecular weight in number Mn of 150 to 10,000 g / mol and which represent XH-functionalized poly (alkylene oxides) whose content of alkylene oxide units with at least three carbon atoms is 40 to 100 mol% relative to the total content of alkylene oxide units,

with the proviso that 20% to 90% of the isocyanate groups of component (a) react with the compounds of the formula (Ia),

(b2) one or more compounds of the formula (Ib)

G- (XH) n (Ib)

where n represents 2 to 4, and G represents an aliphatic group containing at least two carbon atoms, cycloaliphatic and / or aromatic without tertiary amino groups, with average molecular weight in number Mn at most 3000, which may contain the group -O-, -COO-, -CONH-, -S-, and / or -SO2, react in an amount such that they react 0 to 60%, preferably 0 to 45% and particularly preferably 0 to 40% of the groups NCO of the polyisocyanates originally used,

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

E09711814

07-28-2014

with the proviso that as a result of reactions (b1) and (b2), at least 20% and maximum 90% react, preferably 30 to 65% and particularly preferably 40 to 60% of the isocyanate groups of the polyisocyanates used originally, and

(c1) one or more compounds of the general formula (IIa)

Z-Q (IIa)

where Q represents -NH2, -NHR or OH, where R represents an alkyl group, linear or branched, with 1 to 18 carbon atoms, and

Z represents a basic organic residue with at least one tertiary amino group which does not contain reactive groups against isocyanate, and

(c2) optionally one or more compounds of the general formula (IIb)

M-Q (IIb)

where Q represents -NH2, -NHR or OH, where R represents an alkyl group, linear or branched, with 1 to 18 carbon atoms, and

M represents an organic residue with an average molar mass of maximum 1000 g / mol with at least one tertiary polymer and at least one hydroxyl group,

with the proviso that at least 10% of the isocyanate groups of component (a) react with component (c1).

Component

To prepare the addition compounds of the invention, as component (a) polyisocyanates with at least two isocyanate groups per molecule were used. Isocyanates of this type are known in the technical field in question in the prior art.

These are particularly preferably oligomeric or polymeric derivatives of monomeric diisocyanates which have biuret, urethane, uretdione and / or isocyanurate groups. Monomeric diisocyanates of this type are, for example, 1,4-diisocyanatobutane, hexamethylene diisocyanate (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanate-2,2-dimethylpentane, 2,2,4-or 2, 4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanoccyclohexane, 1,3- and 1,4-bis- (isocyanatomethyl) -cyclohexane, 1-isocyanate-3, 3,5-Trimethyl-5-isocyanatomethylcyclohexane (isophorondiisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane, toluylenediisocyanate (TDI), 1-isocyanate-1-methyl-4 (3) isocyanatomethylcyclohexane, bis- (isocyanatomethyl) 1,3 -and 1,4-bis- (2-isocyanate-prop-2-yl) benzene (TMXDI) or mixtures of such diisocyanates. The monomeric isocyanates mentioned can also be used, however, as such alone or in admixture or in admixture with their oligomeric or polymeric derivatives having biuret, urethane, uretdione and / or isocyanurate groups. According to the invention, one or more monomeric, oligomeric or polymeric polyisocyanates can be used.

The polyisocyanates have to have an average functionality of at least 2. The average functionality is preferably at least 2.5 and particularly preferable at least 3. Particularly preferred are the derivatives described previously HDI, TDI and / or IPDI and mainly those of the TDI .

Examples of polyisocyanates of this type are those that can be obtained, for example, by the addition of diisocyanates to polyols such as Desmodur L of the Bayer company or those that can be obtained by reaction of diisocyanate biuret, such as the commercial product Desmodur N of the Bayer company or else the polyisocyanates that can be obtained by cyclisation of diisocyanates with fundamental isocyanurate structure, such as the commercial products Desmodur HL and Desmodur IL of the company Bayer, the commercial products Polurene KC or Polurene HR of the company SAPICI, or trimeric isoforondiisocyanate (Isocianurat T1890 of the Chemische Werke Hüls company). Other examples of polyisocyanates available as commercial products are Desmodur VL (diphenylmethane diisocyanate-based polyisocyanate (MDI), Bayer AG), Desmodur Z 4370 (isophorondiisocyanate-based polyisocyanate (IPDI), Bayer AG), Desmodur N3400 (aliphatic-uretdione HDI, Bayer AG), Thanecure T9 (aromatic TDI-uretdione, TSE Industries), Crelan VP LS 2147 and Crelan VP LS 2347 (aliphatic IDPI-uretdione, Bayer AG), Polurene KD (toluylenediisocyanate-based polyisocyanurate (TDI), SAPICI), Uronal RA.50 (TDI based polyisocyanurate from Galstaff), Polurene A (TDItrimethylolpropane-based polyisocyanate (TMP), SAPICI), MC Polurene (TMP-IPDI-based polyisocyanate, SAPICI), Polurene MD.70 ( Polyisocyanate based on TMP-TDI-MDI, SAPICI). These commercial products are often not found in pure form of a polyisocyanate, but as mixtures of polyisocyanates of similar structure. At the moment

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

E09711814

07-28-2014

invention as polyisocyanates are preferred trimerization products, that is, products of diisocyanates based on hexamethylene diisocyanate (HDI), isophorodiisocyanate (IPDI) and / or toluylene diisocyanate (TDI), which contain one or more isocyanurate groups.

By said "average functionality of at least 2" it is understood that commercial products have the indicated functionality of at least 2 with respect to isocyanate groups. For example, "functionality of 3" means that a molecule contains 3 free isocyanate groups in statistical average.

The average functionality can be determined experimentally by determining the average molecular weight in number Mn and the number of NCO, as described in the examples part of the present application, and calculating from it the equivalent weight of NCO. The average functionality is the ratio of the average molecular weight in number and the equivalent weight of NCO. The average molecular weight of the polyisocyanates is preferably at least 200, preferably at least 300, particularly preferably at least 500. The average functionality is preferably 2.5 to 10, particularly preferably at least 3, as per Example 3 to 6.

Component (b1)

The polyisocyanates of component (a) react according to the invention with compounds of component (b1) of the previous formula (Ia).

The compounds of the formula (Ia) are characterized in that they contain exactly one XH group reactive against isocyanate groups. The compounds of the formula (Ia) react through their XH group reactive irreversibly with the isocyanates.

For group Y of the compound of the general formula (Ia) it is applied that this is not reactive against isocyanates, that is to say that it does not contain reactive hydrogen atoms according to Zerewitinoff. This mainly means that the Y group is free of the previously mentioned XH groups.

Examples of XH are OH, NH2, NHR, SH or COOH, in which case R represents a linear or branched alkyl group having 1 to 18 carbon atoms. XH preferably represents OH, NH2 or NHR. These functional groups are particularly preferably hydroxyl groups because these groups are easily accessible and / or commercially available and the reaction products obtained dissolve well in the solvents that are used according to the invention in the case of a subsequent application. of the additives.

The non-reactive Y groups against isocyanates may have the heteroatoms O, S, Si and / or N and / or the ether, urethane, carbonate, amide and / or ester groups. In the Y groups, hydrogen is optionally substituted by halogen, preferably fluorine and / or chlorine.

As compounds of the formula (la), aliphatic, cycloaliphatic and / or araliphatic compounds can be used. Mixtures of such compounds may also be used, that is to say at least two different compounds of the formula (Ia). The aliphatic or araliphatic compounds of the formula (Ia) can be straight or branched chain. They can be saturated or unsaturated. However, saturated compounds are preferred.

Examples of compounds of the formula (la) are straight or branched chain alcohols such as methanol, ethanol, butanol, ethylhexanol, decanol, iso-tridecyl alcohol, lauryl alcohol, stearyl alcohol, isobornyl alcohol, benzyl alcohol, propargyl alcohol, oleyl alcohol , linolethyl alcohol, oxoalcohols, neo-pentyl alcohol, cyclohexanol, fatty alcohols, alkylphenols, monophenyldiglycol, alkylnaphthols, phenylethanol, hydroxy-functional vinyl compounds, such as, for example, hydroxybutyl vinyl ether, acrylates or methacrylates such as hydroxy-functional, hydroxy-functional, such as hydroxy-functional of hydroxyethyl, hydroxyethyl methacrylates, (meth) hydroxybutyl acrylate as well as polyolefinpolyols such as hydroxy functional polybutadienes, optionally hydrogenated, polypropylenes, ethylene / butylene copolymers or polystyrenes with an average functionality of 1 to 3. Examples of corresponding commercial products are polybutadienes hydrogenated, hydroxytermines, available under the Politail® designation of Mitsuahi Chemical or the hydroxytermined ethylene / butylene copolymers Kraton® Liquid L-1203, L-1302 and L2203 from Kraton Polymers or liquid polybutadienes available as NISSO-PB from Nippon Soda Co. or alcohols linear, long chain, saturated, available in Baker Petrolite as Unilin® Alcohols, largely primary alcohols with chain lengths up to C50 and molecular weights of 375 to 700 g / mol and their ethoxylates available under the Unithox® designation. Other examples are described, among others, in EP-A-154

678. Of the hydroxy compounds mentioned above, those which preferably do not contain polymerizable double bonds are preferred.

As compounds of the formula (Ia), those containing groups of esters, ethers, urethane, carbonate, amide and / or siloxane or combinations of these groups can also be used. They can also be, for example, polyethers, polyesters, polyurethanes, polycarbonates, polysiloxanes or, for example, mixed polyether polyesters.

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

E09711814

07-28-2014

The polyesters can be produced, for example, by reaction of dicarboxylic acids and their sterefiable derivatives, for example, anhydrides, acid chlorides or dialkyl esters, such as dimethyl esters or diethyl esters by reaction with diols and mono functional start components. The esterification can be carried out in bulk or also by azeotropic esterification in the presence of a separating agent. Examples of dicarboxylic acids are succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic acid or dimerized fatty acids and their isomers and hydrogenation products. Examples of diols are: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cis1,2-cyclohexyandimethanol, trans-1,2-cyclohexandimethanol, as well as polyglycols based on ethylene glycol and / or propylene glycol.

Polyesters of the formula (Ia) can also be those that can be obtained by polycondensation of one

or several optionally substituted alkyl hydroxycarboxylic acids and / or ring opening polymerization of the corresponding lactones such as, for example, propiolactone, valerolactone, caprolactone by means of a starting monohydroxy component, as described in EPA-154 678 ( US-A-4 647 647). If these are used, then they preferably have an average molecular weight in Mn number of 150 to 5000 g / mol. As the starting component, in theory all compounds other than those indicated as compounds of the formula (Ia) are useful. The mono functional alcohols used as starting components preferably have 1 to 30, better yet 4 to 14 carbon atoms. By way of example, n-butanol, long chain, saturated and unsaturated alcohols such as propargyl alcohol, oleyl alcohol, linolethyl alcohol, oxoalcohols, cyclohexanol, phenylethanol, neopentyl alcohol, ethylene glycol, propylene glycol and glycerin, but also fluoxylated xyloxy alcohols , functional hydroxy vinyl compounds such as, for example, hydroxybutyl vinyl ether, hydroxy functional acrylates or methacrylates such as, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl (meth) acrylate, hydroxy functional polyalkylene glycol acrylates. It is also possible to convert alcohols of the type described previously and substituted and unsubstituted phenols by alkoxylation according to known processes, using alkylene oxides such as, for example, ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide , in monoalkyl ethers of polyoxyalkylene, monoaryl polyoxyalkylene, monoaralkyl of polyoxyalkylene and monocycloalkyl of polyoxyalkylene and use these hydroxypolyethers in the manner previously described as starting components for the polymerization of lactone. Respective mixtures of the aforementioned compounds may also be used, for example mixtures of lactones; for example of ε-caprolactone and δ-valerolactone. The polymerization of lactones is carried out according to known processes, initiated by, for example, BF3, p-toluenesulfonic acid or dibutyl tin dilaurate, at temperatures of about 70 ° C to 180 ° C. However, component (b1) preferably contains less than 35 mole% of compounds of the formula (Ia), which contain copolymerized lactones or their hydroxycarboxylic acid analogs. Particularly it is preferred that its fraction be less than 20% molar. Very particularly preferable, component (b1) does not contain compounds of the general formula (Ia), which contain copolymerized lactones or their hydroxycarboxylic acid analogs.

Preferred compounds of the formula (Ia) are hydroxy functional polyethers, hydroxy functional polyesters, hydroxy functional polyether polyethers and / or aliphatic and / or cycloaliphatic alcohols with 2 to 30 carbon atoms, their hydrogen atoms are optionally partially replaced by halogen and / or residues from arilo.

As compounds of the formula (Ia), monofunctional polysiloxanes can also be used, such as, for example, monoamine or monohydroxyfunctional polyalkylsiloxanes, which do not contain hydroxyl groups bonded with silicon or aminoalkylpolysiloxane atoms which may optionally be modified with polyether and / or polyester. The respective aminofunctional compounds have in this case primary or secondary amino groups although not tertiary. It is preferred to employ hydroxyalkylpolydimethylsiloxanes with average molecular weights in Mn number of 400 to 8000 g / mol, particularly preferably 400 to 5000 g / mol and very particularly preferably 400 to 2000 g / mol.

As compounds of the formula (Ia), polyurethanes, polyether polyurethanes, polyesters polyurethanes and / or polyether polyesters polyurethanes can also be used, which can be produced by adding diisocyanates with dihydroxy compounds in the presence of starting monofunctional components.

As the diisocyanate to synthesize the compounds containing urethane groups of the formula (Ia), aliphatic, cycloaliphatic and / or aromatic diisocyanates with 4 to 15 carbon atoms known per se from polyurethane chemistry, such as tetramethylene diisocyanate, hexamethylene diisocyanate, can be used. , trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, isophorondiisocyanate, toluylene diisocyanate, diphenylmethane diisocyanate, methylenebis (-4-cyclohexyl isocyanate) or 1,4-cyclohexanbis (methyl isocyanate). As hydroxy compounds to synthesize the compounds having urethane groups according to formula (Ia) preferably diols with 2 to 12 carbon atoms, polyoxyalkylene glycols and dihydroxy functional polyesters with preferred number average molecular weights Mn of at most 2000 g / mol are used . As starting monohydroxy functional components, alcohols with up to 30 carbon atoms can be used, as already described for the preparation of the polyesters of the formula (Ia), although also the hydroxy polyesters and hydroxy polyethers described as a compound according to the formula (Ia). The polyesters preferably have an average molecular weight in Mn number of 300 to 5000 g / mol and the polyethers of 200 to 2000 g / mol.

fifteen

25

35

Four. Five

55

E09711814

07-28-2014

The Y residue may also contain carbonate groups as obtained by reaction according to the state of the art with open chain and / or cyclic carbonates. For example, linear polyesters modified with carbonates or polycarbonate diols are suitable, as used in the preparation of polyurethanes. Examples are described in US 410 152 9, EP 0358 555, or WO 02/085507. Suitable carbonates are, for example, aliphatic, cycloaliphatic, araliphatic and / or aromatic esters of carbonic acid such as, for example, dialkyl carbonates such as dimethyl carbonates, diethyl carbonates or diphenyl carbonate, catechol carbonate or cyclic alkylene carbonates. Particularly suitable are cyclic alkylene carbonates with 5 or 6 member rings which may be optionally substituted. Aliphatic, cycloaliphatic and / or aromatic groups with up to 30 carbon atoms are preferred as substituents. Examples of suitable cyclic alkylene carbonates are ethylene carbonate, propylene carbonate, glycerin carbonate, trimethylene carbonate, 4-methyltrimethylene carbonate, 5-methyltrimethylene carbonate, 5,5-dimethyltrimethylene carbonate, 5,5-methyltrimethylene carbonate or carbonate of 5-methyl-5-propyltrimethylene.

The Y residue may have other groups that behave inertly during the formation of the addition product, such as, for example, the carboxamide group (-NHCO-), non-activated double bonds or urea groups (-NHCONH-). The fraction of the compounds of the formula (Ia), which carry such groups must be, with respect to all the compounds used in the formula (la) preferably below 40 mol%, preferably below 5 mol%. Particularly preferred are compounds that do not contain any of these groups.

The ester, ether, urethane, carbonate and / or siloxane groups optionally present may be in block structure (for example, poly (ethylene oxide-propylene oxide-epsilon-caprolactone block), form a gradient or be arranged randomly.

As the compound of the formula (Ia), polyacrylates and / or polymethacrylates with, on average, an isocyanate reactive group can also be used, as obtained by anionic, cationic or free radical polymerization of the acrylic acid esters or esters of methacrylic acid Monohydroxy functional compounds are preferred. Monohydroxy functional polyacrylates or polymethacrylates are those that contain on average a hydroxyl group in the molecule. Such compounds have already been used in this field of technology to prepare other dispersants such as, for example, those described in US-A-4 032 698 or in EP 318 999. These polyacrylates preferably have a number average molecular weight Mn from 300 to 20,000 g / mol, more preferably from 500 to 10,000 g / mol. They can be arranged in a block structure or also randomly or they can form a gradient.

The carboxyl group of the monomeric acrylates or methacrylates can be esterified, for example, with aliphatic, cycloaliphatic and / or aromatic alcohols such as methanol, butanol, cyclohexanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, isobornyl alcohol, benzyl alcohol or with alcohols of ether such as 2-methoxyethanol, 2-phenoxyethanol, tetrahydrofurfuryl alcohol or glycidol, with polyester alcohols such as hydroxy functional polycaprolactone,

or with alkoxypolyalkylene glycols such as methoxypolyethylene glycol or methoxypolypropylene glycol. Methoxy polypropylene glycols are preferred as alkoxypolyalkylene glycols. The average molecular weight in number Mn of the esterification component is preferably below 2000 g / mol. Mixtures of the different monomers described previously can also be used to produce hydroxy-functional polyacrylates or polymethacrylates. To produce these polyacrylates or polymethacrylates, vinyl esters such as vinyl acetate, vinyl esters such as vinyl ether, styrene, vinyl toluene and / or vinylcyclohexane can also be used as comonomers. The copolymers obtained in this way were synthesized in this case from preferably no more than 50 mol% of comonomers with acrylic functionality.

The poly-2-alkyl-2-oxazolines or hydroxy-functional poly-2-alkyl-2-oxazines can also go as a compound of the formula (Ia). Preferably monohydroxy functional compounds are used. Poly-2-alkyl-2-oxazolines or poly-2-alkyl2-oxazines are obtained, as is known to the person skilled in the art, by ring opening polymerization of 2-alkyl-2-oxazolines or 2-alkyl- 2-oxazines with initiators such as, for example, paratoluenesulfonic acid, methyl tosylate or methyl triflate. The oxazolinium or oxazinium groups resulting from the live cationic polymerization mechanism can be converted to the most stable hydroxyamides by alkaline hydrolysis by means of amino ester end groups. An alternative route to produce poly-2-alkyl-2-oxazolines or monohydroxy-functional poly-2-alkyl-2-oxazines is the polymerization with 2- (4-hydroxyphenyl) -N-methyl-2oxazolineotrifluoromethane sulfonate as the initiator species. (A. Groß, G. Maier, O. Nuyken, Macromol. Chem. Phys. 197, 2811-2826 (1996)). By selecting the alkyl substituents it is possible to control the compatibility; Thus, for example, poly-2-ethyl-2-oxazoline is suitable for highly polar systems because of its water solubility, while, for example, poly-2-lauryl-2-oxazoline is compatible in apolar systems. If block copolymers are formed from 2-ethyl-2-oxazoline and 2-lauryl-2-oxazoline, then the polymers are characterized by a particularly broad compatibility. Such poly-2-alkyl-2-oxazolines or poly-2-alkyl-2-oxazines preferably have an average molecular weight in Mn number of 300 to 20,000 g / mol, more preferably 500 to 10,000 g / mol.

As compounds of the formula (Ia), mono-XH-functional poly (alkylene oxides) can also be used. These can be obtained, for example, by alkoxylation of other compounds described other than

fifteen

25

35

Four. Five

55

E09711814

07-28-2014

compounds of the formula (Ia) such as, for example, alkanols, cycloalkanes, phenols or the hydroxy polyesters previously described with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or mixtures thereof. In the case of mixed polyethers, these may be arranged randomly, as a gradient or in blocks. These polyethers conveniently have a number average molecular weight (Mn) in the range of about 100 to 10,000, preferably 150 to 5000 and particularly preferably 200 to 3500 g / mol. Polyethers based on ethylene oxide, propylene oxide and butylene oxide and mixtures thereof are preferred. In addition, monohydroxy functional polyoxyalkylene mono alcohols are preferred as allyl polyethers, for example Polyglycol A 350, Polyglycol A 500, Polyglycol A 1100, Polyglycol A 11-4, Polyglycol A 20-10 or Polyglycol A 20-20 from Clariant AG or Pluriol® A 010 R , Pluriol® A 11 RE, Pluriol® A 13 R, Pluriol® A 22 R or Pluriol® A 23 R from BASF AG, vinyl polyethers, for example Polyglicol V 500, Polyglycol V 1100 or Polyglycol V 5500 from Clariant AG, polyoxyethylene mono alcohols prepared from methanol, for example Pluriol® A 350 E, Pluriol® A 500 E, Pluriol® A 750 E, Pluriol® A 1020 E, Pluriol® A 2000 E or Pluriol® A 5010 E from BASF AG, polyoxypropylenemonoal alcohols prepared from alkanol, for example Polyglycol B01 / 20, Polyglycol B01 / 40, Polyglycol B01 / 80, Polyglycol B01 / 120 or Polyglycol B01 / 240 from Clariant AG or Pluriol® A 1350 P or Pluriol® A 2000 P from BASF AG, and poly- alkoxylates prepared from different fatty alcohols with varying degrees of al coxylation, as is known to those skilled in the art under the trade names Lutensol® A, Lutensol® AT, Lutensol® AO, Lutensol® TO, Lutensol® XP, Lutensol® XL, Lutensol® AP and Lutensol® ON from BASF AG . It is preferred to use polyoxyalkylene mono alcohols containing ethylene oxide and / or propylene oxide and / or butylene oxide groups which are optionally modified with styrene oxide. Particularly preferred is the use of polyoxyalkylene mono alcohols such as, for example, Polyglycol B 11/50, Polyglycol B 11/70, Polyglycol B 11/100, Polyglycol B 11/150, Polyglycol B 11/300 or Polyglycol B 11/700 of Clariant AG , Pluriol® A 1000 PE, Pluriol® A 1320 PE, or Pluriol® A 2000 PE from BASF AG or Terralox WA 110 from DOW Chemicals, which are polyoxyalkylenes prepared from butanol, ethylene oxide and propylene with an OH group terminal. Of the previously mentioned compounds, those that do not contain polymerizable double bonds are preferred.

Component (b1) must contain at least 55% molar, preferably at least 75% molar and particularly preferably 100% molar of compounds of the general formula (la), which are functionalized poly (alkylene oxides) XH and have a weight Average molecular number in Mn number from 150 to 10,000 g / mol, preferably at least 300 g / mol, particularly preferable at least 600 g / mol and very particularly preferable at least 1000 g / mol. The upper limit of the maximum molecular weight Mn is preferably at most 5000 g / mol, particularly preferable at most 3000 g / mol and very particularly preferable at most 2000 g / mol. These compounds have to have an alkylene oxide unit content with at least three carbon atoms of 40 to 100 mole%, preferably at least 55 mole percent, particularly preferably at least 60 mole percent, very particularly preferably at least 65 mole percent and in a particularly preferred 100% molar modality with respect to the total content of alkylene oxide units. Alkylene oxide units with at least three carbon atoms are preferably derived from propylene oxide and butylene oxide. Particularly preferred is the use of compounds based on poly (propylene oxide) and monohydroxy-functional poly (propylene oxides) prepared from butanol are very particularly preferred. As a comonomer with less than three carbon atoms, ethylene oxide is taken into account. These compounds are prepared as described in the preceding section, preferably by alkoxylation of monohydroxy functional compounds. Preferably these do not contain polyester fractions, mainly they do not contain polyester fractions derived from lactones or hydroxycarboxylic acids and are preferably free of polymerizable double bonds.

In applications where broad compatibility is required, for example, in the field of universal pastes, it is often advantageous to use addition compounds that are prepared with mixtures of different compounds of the formula (la). If the addition compounds of the invention are used in universal dye pastes, for example, for aqueous and non-polar systems, a combination of water-soluble compounds with apolar compounds of the formula (Ia) is advantageous.

The average molecular weight in number Mn of the compound Y-XH is less than 20,000 g / mol and preferably finds a maximum of 10,000 g / mol, particularly preferably a maximum of 5000 g / mol, very particularly preferably a maximum of 3,500 g / mol and even better in maximum 2000 g / mol. The minimum molecular weight Mn of Y-XH is preferably 100 g / mol, particularly preferable 150 g / mol, very particularly preferable 200 g / mol and best 400 g / mol. Preferably less than 50 mol% of the compounds of the formula (la) has a number average molecular weight less than 100 g / mol, particularly preferably less than 25 mol%, very particularly preferably less than 15 mol% and of the best 0% molar way.

In the reaction with the monofunctional compounds of the formula (Ia), they react from 20% to 90%, preferably from 20% to 70% and particularly preferably from 25% to 60% of the free NCO groups originally used.

Component (B2)

The compounds of the general formula (Ib) G- (XH) n with n = 2 to 4, are distinguished from those of the formula (la) essentially in that they contain two, three or four functional XH groups, defined independently of whether, which are reactive against isocyanates. Among the XH groups are the same preferred as for the

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

E09711814

07-28-2014

formula (Ia). The average molecular weight in number Mn of the compounds of the formula (Ib) is less than 3000 g / mol and is preferably at most 2500 g / mol, particularly preferably at maximum 2000 g / mol, very particularly preferably at maximum 1500 g / mol. The minimum molecular weight Mn of the compounds of the formula (Ib) is preferably 100 g / mol, particularly preferable 150 g / mol, very particularly preferable 300 g / mol and best 600 g / mol.

Examples of di-, tri-and tetrafunctional compounds of the formula (Ib) are triols, triols and tetraols or diamines, triamines and tetraamines without tertiary amino groups having 2 to 12 carbon atoms, dihydroxydialkyl sulfides and dihydroxysulfones. Examples are butanediol, hexandiol, cyclohexanedimethanol, neopentyl glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, dialkanolamides of fatty acid, thiodiglycol, di (4-hydroxyphenyl) sulfone as well as hydroxyfunctional polybutadienes with an average group of 2 compounds. of the formula (Ib) are polyoxyalkylene glycols particularly preferable with two alkylene groups having 2 to 4, very particularly preferably two carbon atoms and preferably with average molecular weights in Mn number in the range of 200 to 2000 g / mol, particularly preferably 400 to 1500 g / mol. Ethoxylates with 3 hydroxyl groups are obtained by polymerization, for example, using trifunctional alcohols as initiator components. As polyoxyalkylene glycols, polyethylene glycols are preferred.

As di-, tri-or tetrafunctional compounds of the formula (Ib), those which can be obtained by polymerization of one or more lactones can also be used in theory, as already mentioned, by di-, tri- or tetrahydroxy-initiating components. These polyester polyols preferably have an average molecular weight in Mn number of 500 to 2000 g / mol. Butandiol or ethylene glycol is preferred as the initiating component. But the above-mentioned diols, triols or tetraols are also considered as initiating components. Component (b2) preferably contains less than 50 mol%, particularly preferably less than 20 mol% and most particularly preferably does not contain polyester polyols, mainly does not contain polyester polyols based on lactones or their hydroxycarboxylic acid analogs.

As polyfunctional compounds of the formula (Ib), polyurethanes, polyethers-polyurethanes, polyesters-polyurethanes and / or polyethers-polyesters-polyurethanes which can be obtained by reaction of adding a diisocyanate with a dihydroxy-compound analogously to the compounds can also be used. corresponding monofunctional of the formula (Ib). These urethane-containing compounds according to formula (Ib) preferably have an average functionality of maximum 2 and a number average molecular weight of 300 to 2500 g / mol, preferably 500 to 1500 g / mol.

The di-, tri-or tetrafunctional compounds of the formula (Ib) cause a cross-linking between the polyisocyanate reaction products and monofunctional compounds of the formula (Ia). For example, the starting products can be used in amounts such that the di-, tri-or tetrafunctional compounds of the formula (Ib) represent the center of the molecule and are linked to the polyisocyanates whose remaining isocyanate groups have reacted or react with monofunctional compounds of the formula (I). Of course it is also possible that excessive crosslinking or insufficient crosslinking occurs.

In the case of reaction with the di-, tri- or tetrafunctional compounds of the formula (Ib), 0 to 60%, preferably 0% to 45%, and particularly preferably 0% to 40% of the NCO groups originally used are reacted .

Particularly preferred products are obtained completely without using di-, tri- or tetrafunctional compounds of the formula (I).

In total at least 20%, particularly preferably at least 25 and maximum 90%, preferably maximum 80%, particularly preferably maximum 70%, of the NCO groups originally used from the polyisocyanate of component (a) react with the compounds of the formula (I ).

The reaction of the polyisocyanates with different compounds of the formulas (Ia) and (Ib) can be carried out in a single reaction step or in two or more reaction steps successively. This can happen in any order. In many cases it is advantageous, however, to react the polyisocyanate successively with the components in the first order of the monofunctional components (formula (Ia)) and then the polyfunctional compounds (formula (Ib)). The addition of isocyanate, depending on the reactivity of the individual reagents, can be carried out in the usual temperature range for this type of reaction, from room temperature to about 150 ° C. In order to accelerate and reduce secondary reactions, known and customary catalysts such as tertiary amines such as, for example, triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) can be used according to the state of the art ) -ethanol, diazabicyclo- (2,2,2) octane and the like, as well as mainly organometallic compounds such as, for example, titanates, iron compounds such as, for example, iron (III) acetylacetonate, tin compounds, for example tin diacetate, tin dioctoate, tin dilaurate dialkyl derivatives of dialkyl tin salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate or the like. These catalysts are usually used in amounts of 0.0001 to 0.1 parts by weight per 100 parts by weight of polyisocyanate.

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

E09711814

07-28-2014

Component (c1)

The component (c1) is represented by the general formula (IIa) as Z-Q. The Z group is a basic organic residue with at least one tertiary amino group that does not contain NCO reactive groups. The residue Z is preferably a cycloaliphatic aliphatic group with at least one tertiary amino group optionally in the form of a tertiary ring nitrogen atom of a heterocyclic ring system. The tertiary amino group or the heterocyclic ring system with tertiary ring nitrogen may be linked directly to the Q group or through an organic bridge group ("spacer"). The spacer, through which the tertiary amino group or the heterocyclic ring system with tertiary ring nitrogen may be attached to the group Q, preferably comprises 2 to 10, more preferably 2 to 5 carbon atoms. Particularly preferred is an alkylene group having 2 to 10, most preferably 2 to 5 carbon atoms, or a polyether group having the same number of carbon atoms. The group Q represents NH2, OH or NHR, where R represents a linear or branched alkyl group with 1 to 18 carbon atoms.

A group of compounds that can be used as ZQ compounds of the formula (IIa), is composed of monohydroxyamines with a tertiary amino group or aliphatic diamines with a tertiary amino group and a first or second amino group such as, for example, (N, N-diethylamino) ethanol, (N, N-dimethylamino) ethanol, (N, N-dimethylamino) propanol, 2- (diethylamino) ethylamine, 3- (dimethylamino) propylamine, 3- (diethylamino) propylamine, N, N-diethyl1,4 -butandiamine, 1-diethylamino-4-aminopentane, of which 3- (dimethylamino) propylamine and (N, N-diethylamino) ethanol are preferred.

In the case of another group, Z represents a mono- or bicyclic heterocyclic group, of which a ring nitrogen atom is linked to the group Q preferably through an alkylene group with 2 to 5 carbon atoms. Preferred heterocycles are triazole, pyrimidine, imidazole, pyridine, morpholine, pyrrolidine, piperazine, piperidine, benzimidazole, benzothiazole and / or triazine, and imidazole and benzimidazole are particularly preferred. These heterocycles may have one or more substituents. They preferably have one of the following groups: alkyl and / or alkoxy groups with 1 to 6, preferably 1 to 4 carbon atoms (in which case a methoxy group is preferred) or tertiary amino groups.

It is preferred that the heterocyclic groups are linked group Q through a ring nitrogen atom and an alkylene group preferably with 2 to 5 carbon atoms. The heterocyclic group, in addition to this ring nitrogen atom, can naturally have other hetero atoms, including other ring nitrogen atoms.

Other examples of compounds of the formula (IIa) are N- (3-aminopropyl) imidazole, N- (3-aminopropyl) morpholine, N- (2-aminoethyl) piperidine, 1-methylpiperazine, aminoethylpiperazine. For these compounds it is characteristic that they contain per molecule at least 1 reactive group with at least 1 Zerewitinoff hydrogen atom, which can react with the NCO groups, which also have a basic group containing nitrogen without reactive hydrogen. In the prior art, these basic groups are characterized by their pKa value (compare US-A3,817,944; 4,032,698 and 4,070,388). Compounds with basic groups having a pKa value of 2 to 14, particularly preferable of 5 to 14, and very particularly preferable of 5 to 12 are preferred. The pKa value can be taken from tables. The limit values indicated previously refer to the measurement of the pKa value at 25 ° C molar at a concentration of 0.01 molar in water. These basic groups also confer basic properties to the addition compounds of the invention.

For example, compounds of the formula Z-Q can be obtained by reacting a (meth) acrylate or epoxide with an amine or nitrogen-containing heterocyclic ring system. Examples of reaction products between a (meth) acrylate and nitrogen-containing heterocyclic ring systems are the reaction products of the hydroxyethyl and hydroxypropyl esters of the (meth) acrylic acid with the nitrogen-containing heterocyclic ring structure, in which case the Following structural elements adhere to the nitrogen of the heterocyclic ring structure:

2-hydroxyethyl propionic acid ester, 2-hydroxypropyl acid propionic acid 2-methylpropionic acid 2-hydroxyethyl ester and 2-methylpropionic acid 2-hydroxypropyl acid ester and ethoxylated and / or propoxylated derivatives thereof. Acrylic acid esters are preferred.

The reaction with amines proceeds analogously.

By reacting an epoxide with an amine or a nitrogen-containing heterocyclic compound, compounds Z-Q can also be obtained. During the reaction, as a group Q a secondary hydroxyl group is formed and a tertiary amino group participates in the nitrogen atom.

Component (c2)

As compounds M-Q according to formula (IIb) compounds are used where M represents an organic residue with an average molar mass in a maximum number of 1000 g / mol, preferably a maximum of 500 g / mol and

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

E09711814

07-28-2014

particularly preferable of 300 g / mol, which contains at least one tertiary amino group and at least one OH group, and where Q represents NH2, NHR or OH (in which case R represents a linear or branched alkyl group with 1 to 18 atoms carbon)

Preferably, M contains 1 to 10, particularly preferably 1 to 5, and very particularly preferably 1 to 3, such as 2 OH groups. Primary OH groups are preferred.

Examples of MQ with tertiary amino groups and OH groups are triethanolamine, N-methyldiethanolamine, aminopropylmethylene ethanolamine, 3- (diethylamino) propan-1,2-diol, tetrakis (2-hydroxypropyl) ethylenediamine, bis (2-hydroxyethyl) dodecylamine, bis (2- hydroxyethyl) octadecylamine.

The compounds of the component (c2) can be produced analogously to the compounds of the component (c1) by reaction of (meth) acrylates or epoxides with amines. If, for example, glycidol is used as an epoxide, which already contains a primary hydroxyl group, then by reaction with a secondary amine, a tertiary amine and secondary hydroxyl groups are additionally formed so that addition products of this type have a primary and a secondary hydroxyl group as well as a tertiary amino group.

Heterocycles containing nitrogen can react analogously with (meth) acrylates and epoxides.

Mixtures of different starting substances can also be used to produce addition compounds according to the invention, such as mixtures of (a) polyisocyanates, and / or components (b1) or (b2) and / or components (c1). Individual representatives of several of the components (a), (b1), (b2) or (c1) can be used in excess or in default. However, the quantity ratios are preferably selected such that in essence the isocyanate groups completely react, which is understood to preferably convert at least 90%, particularly preferably at least 95%, very particularly preferably at least 98% and optimally all isocyanate groups.

By virtue of the basic groups, the addition compounds are capable of forming salts. In the context of the invention, as dispersants they can also be used in the form of corresponding salts. In some cases, through such, partial or total salinization, an improvement in effectiveness and / or better solubility or compatibility can be achieved. Even in applications where the basic ownership of products is an obstacle, for example in acid catalyzed systems, improvements can often be achieved by partial or total neutralization.

The salts are obtained from the reaction product by neutralization with one or more organic or inorganic acids or by quaternization. The amount of acid to use depends on the field of application. Depending on the individual case, the acid components can be used equimolarly, in default or in excess. Of the polycarboxylic acids, for example, up to one equivalent of polycarboxylic acid can be used for a basic group to be neutralized in order to give the products an acid character. Preferably it is neutralized to approximately equimolar. Salts with organic carboxylic acids or acidic esters of phosphoric acid are preferred. Examples of such phosphoric acid acid esters are described in EP 893 155, EP 417 490 and US 5 143 952. Examples of carboxylic acids are aliphatic and / or aromatic carboxylic acids such as short or long chain fatty acids, formic acid, acetic acid , neodecanoic acid, oleic acid, pine oil fatty acid, stearic acid, ricinoleic acid, natural, saturated or unsaturated fatty acids, of vegetable or animal origin and their addition products of maleic anhydride, maleic acid, fumaric acid, succinic acid , dodecylsuccinic acid, 5-norbornene 2,3-dicarboxylic acid, adipic acid, glutaric acid, benzoic acid, nitrobenzoic acid, phthalic acid, tetrahydrophthalic acid, isophthalic acid, terephthalic acid, dimerized or trimerized fatty acids, citric acid and abietic acid.

The addition compounds according to the invention preferably do not contain ethylenically unsaturated groups.

In addition, the addition compounds of the invention are preferably prepared from components that are not based on lactones, primarily are not based on caprolactone, that is, from components (a), (b1), optionally (b2) , (c1) and optionally (c2), for whose own preparation no lactones were used, mainly caprolactones (or the corresponding hydroxycarboxylic acid).

By using polyisocyanates whose use is preferred with, on average, at least 2.5 free isocyanate groups, branched polyurethane structures, ie non-linear, are formed. Accordingly, according to the invention, non-linear addition compounds are particularly preferred.

The preparation of the addition compounds of the invention can be carried out, depending on the viscosity, by mass or in the presence of suitable solvents, mixtures of solvents or other suitable vehicles. All solvents or vehicles that are not reactive under the selected reaction conditions or that their reactivity can be neglected against that of the reagents and in which the reactants and the products of

fifteen

25

35

Four. Five

55

E09711814

07-28-2014

reaction are at least partially soluble. These include, for example, hydrocarbons such as toluene, xylene, aliphatic fractions and / or aliphatic benzine cycles, chlorinated hydrocarbons such as chloroform, trichloroethane, cyclic and acyclic ethers such as dioxane, tetrahydrofuran, dialkyl polyalkylene glycol ethers such as dimethyl glycol dipropyl ether, of mono-, di- or polycarboxylic acids such as ethyl acetate, butyl acetate, butyrolactone, dimethyl-2-methyl glutarate, triacetin, phthalate, two other plasticizers, di- or polycarboxylic acid esters, dialkyl esters, called "esters dibasic ", of C2-C4 dicarboxylic acids, alkyl glycol esters such as ethyl glycol acetate, methoxypropyl acetate, ketones such as methyl isobutyl ketone, cyclohexanone, acetone, acidic amides such as dimethylformamide, N-methylpyrrolidone and the like. The solvent (s) or vehicles are conveniently selected considering the planned field of application. For example, for addition compounds of the invention for use in water-dilutable paint systems or for aqueous suspension coating pigments after pigment synthesis it is preferred to use solvents that are totally or partially water-dilutable. If the products, for example, are to be used where the presence of VOC (volatile organic compounds) is not desired, as soon as possible the formulation should be solvent free or present in vehicles with corresponding high boiling point.

Depending on the field of application, it is possible that the solvents used for the synthesis remain in the reaction mixture or that they are totally or partially removed and optionally replaced by other solvents or vehicles. The addition compounds of the invention can be combined depending on compatibility even with resins, resin solutions, reactive diluents, binders or with other additives known in the state of the art, such as other humectants and dispersants, anti-settling agents , surfactant additives such as silicones and the like.

The solvent can be totally or partially removed, for example, by distillation, optionally under reduced pressure and / or azeotropic by adding water. However, the active substance can also be isolated by precipitation by adding non-solvents such as aliphatic hydrocarbons, for example hexane, by subsequent separation by filtration and optional drying. The active substance obtained according to these methods can then be diluted in a solvent suitable for the respective field of application or optionally used in pure form, for example, in powder paints. Optionally, the solvent in which the addition product is dissolved can be distilled after adding suitable solvents with a higher boiling point, optionally under reduced pressure and / or azeotropically adding water, in this way the addition product can be transferred to a vehicle that is suitable for the respective field of application.

The reactions can be carried out in the presence of usual catalysts, such as, for example, organic tin compounds such as dibutyl tin dilaurate, other metal organ compounds such as iron acetylacetonate, tertiary amines such as triethylenediamine, enzymes or the like.

By variation of the substituents of the formula (Ia), with respect to their type, quantity ratios and / or molecular weights, the properties of the addition compounds of the invention can be adapted to the different fields of application. Thus, for example, solubility and compatibility can be combined with the most diverse solvents, vehicles, binders, resins, solids and optionally other polymeric compounds, which are present in coating and molding compositions, in which they are used. the addition compounds of the invention.

For use in highly polar systems such as, for example, aqueous paints, the Y residues must include a sufficiently high fraction of polar groups such as poly (ethylene oxides), for example, in order to achieve a level of water solubility that is sufficient to The particular area of use. This fraction of hydrophilic groups should also not be too high if in this way, in certain applications, this results in an unwanted elevation of water sensitivity. In an important embodiment, the Y residues of the XHfunctionalized poly (alkylene oxides) are moieties that essentially confer hydro-solubility to the Y-XH compounds and also, ultimately, to the addition compounds of the invention. Such Y moieties of the XH functionalized poly (alkylene oxides) conveniently contain a maximum of 28% by weight, preferably a maximum of 20% by weight, particularly preferably a maximum of 10% by weight and very particularly a maximum of 5 % by weight of ethylene oxide units with respect to the total content of alkylene oxide units in residue Y.

When used in apolar systems such as alkyd paints of large amounts of oil, PVC plastisols or polyolefins, preferably a corresponding fraction of apolar groups should be present, and when used in systems in which broad compatibility is important, for example in concentrates of pigments, a balanced combination of polar and apolar groups is advantageous.

For dispersion in silicone oil such as decamethylcyclopentasiloxane, for example, for cosmetic preparations, for example, addition compounds containing polydimethylsiloxane are particularly suitable. If the addition compounds are used in a polyurethane resin, for example, or in a lacquer whose binder is a polyurethane, it is convenient to use such addition compounds of the invention than in its molecule, by virtue of the groups contained in the compounds of formulas (Ia) and (Ib), are also contained

10

fifteen

twenty

25

30

35

40

Four. Five

E09711814

07-28-2014

urethane groups or similar groups that are compatible with polyurethanes, as the person skilled in the art knows. The same applies, in this regard, to polyacrylates, polyesters, alkyd resins and other polymers, for example.

In this regard, this also applies to the substituents of components (c1) and (c2), which have a particular influence on the affinity of the addition compounds of the invention for the solids used to be dispersed.

Addition compounds of the invention with surfactant substituents can modify the surface tension of the substrates prepared therewith. If, for example, very non-polar groups are present, such as long chain alkyl groups with more than 12 carbon atoms, groups containing polydimethylsiloxane and / or containing perflouralkyl, the products are suitable for reducing the surface tension of systems organic or aqueous solids or solid systems, and to influence properties related to this such as, for example, wetting properties, the ability to get dirty, to print, flow and foam behavior. In systems that have a reactivity with OH groups, COOH groups and / or double bonds, for example two-component systems based on isocyanate or melamine resin, systems containing epoxide, coatings that cure with irradiation, such as paints and printing inks which cure with UV or electron beam or unsaturated polyester systems, using addition compounds of the invention with reactive groups such as OH groups, COOH groups and / or unsaturated groups, co-crosslinking can be achieved leading to adhesion enhancements, the incorporation of solids, mechanical properties and migration behavior. In applications where the presence of double bonds leads to undesired disadvantages such as discoloration, as a result of high processing temperatures, for example, it is advantageous to use addition compounds of the invention with unsaturated groups as few as possible and preferably without unsaturated groups.

The average molecular weight in number Mn of the addition compounds of the invention is preferably at least 500 g / mol, particularly preferably at least 800 g / mol, very particularly preferable at least 1200 g / mol and ideally at least minus 2000 g / mol.

Another object of the invention is a method for preparing addition compounds of the invention, in which a reaction of

(a) one or more polyisocyanates with at least two isocyanate groups per molecule with

(b1) one or more compounds of the formula (Ia)

Y-XH (Ia)

where

XH represents a reactive group against isocyanates and

Y represents a monomeric or polymeric group, not reactive to isocyanates, without tertiary amino groups, comprising one or more aliphatic, cycloaliphatic and / or aromatic groups,

in which case the compound of the general formula (Ia) has an average molar mass in number Mn less than 20,000 g / mol and

in which case at least 55% molar of the compounds of the formula (Ia) have an average molecular weight in Mn number of 150 to 10,000 g / mol and which represent XH-functionalized poly (alkylene oxides), whose content of units of alkylene oxide with at least three carbon atoms is 40 to 100 molar relative to the total content of alkylene oxide units,

with the proviso that 20% to 90% of the isocyanate groups of component (a) react with the compounds of the formula (Ia),

(b2) one or more compounds of the formula (Ib)

G- (XH) n (Ib)

where n represents 2 to 4, and G represents an aliphatic, cycloaliphatic and / or aromatic group containing at least 2 carbon atoms, without tertiary amino groups, with an average molecular weight in number Mn at most 3000, which can containing groups -O-, -COO-, -CONH-, -S-, and / or -SO2-, react in such an amount that it becomes

10

fifteen

twenty

25

30

35

40

Four. Five

E09711814

07-28-2014

0 to 60%, preferably 0 to 45% and particularly preferably 0 to 40% of the NCO groups of the polyisocyanates originally used,

with the proviso that reactions (b1) and (b2) react in total at least 20% and maximum 90%, preferably 30 to 65% and particularly preferably 40 to 60% of the isocyanate groups of the polyisocyanates originally used, and

(c1) one or more compounds of the general formula (IIa)

Z-Q (IIa)

where Q represents -NH2, -NHR or OH, where R represents a linear or branched alkyl group with one to 18 carbon atoms,

Y

Z represents a basic organic residue with at least one tertiary amino group, which does not contain reactive groups against isocyanate, and

(c2) optionally one or more compounds of the general formula (IIb)

M-Q (IIb)

where Q represents -NH2, -NHR or OH, where R represents a linear or branched alkyl group with 1 to 18 carbon atoms, and

M represents an organic residue with a number average molecular mass of maximum 1000 g / mol with at least one tertiary amino group and at least one hydroxyl group,

with the proviso that at least 10% of the isocyanate groups of component (a) react with component (c1).

The components (a), (b1), (b2), (c1) and (c2) used in the method according to the invention correspond to those that have been previously described.

The process according to the invention is preferably carried out in such a way that the compounds of component (a) are first reacted with those of component (b1) and optionally (b2) and only then the remaining isocyanate groups react with the compounds of the component (c1).

It is also advantageous to first react the compounds of the formula (la) of the component (b1) with the polyisocyanate component (a) and only then carry out a reaction with the compounds of the formula (Ib) of the component (b2) .

Another object of the invention is the use of the addition compounds of the invention previously described as humectants or dispersants and as dispersion stabilizers.

Also subject to the invention are solid substances with a powder or fiber form that are incorporated into liquid systems which are coated with these addition compounds as dispersants and as dispersion stabilizers or as humectants.

The addition compounds of the invention can be used in place of the dispersants, dispersion stabilizers or humectants known in the state of the art. In this way these can be used, for example, in the preparation or processing of paints, printing inks, inks, for example for inkjet printing, paper coating, leather and textile colors, pastes, pigment concentrates, ceramics and cosmetic preparations, especially if they contain solids such as pigments and / or fillers. They can also be used in the production or processing of compositions for molding based on synthetic, semi-synthetic or natural macro molecular substances, such as for example polyvinyl chloride, saturated or unsaturated polyesters, polyurethanes, polystyrenes, polyacrylates, polyamides, resins epoxies, polyolefins such as polyethylene or polypropylene, for example. For example, it is possible to use the addition compounds to prepare compositions for molding, PVC plastisols, gelcoats (gel-like coatings), polymer concrete, printed circuit boards, industrial paints, wood and furniture varnishes, vehicle paint, boat paints, anti corrosive paints, tin and coil coatings, decorative paints and

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

E09711814

07-28-2014

construction paints, in which case binders and / or solvents, pigments and optionally fillers, the usual addition compounds and auxiliaries are mixed.

Addition compounds are preferably used to produce pigment concentrates, paints, pastes and / or molding compositions containing pigments and / or fillers.

Examples of common binders are polyurethane based resins, cellulose nitrate, cellulose acetobutyrates, alkyd resins, melamine, polyesters, chlorinated rubbers, epoxides and acrylates. Examples of water-based coatings are cathodic or anodic electrodeposition varnishes, for example for car bodies. Other examples are induced, silicate paints, emulsion paints, aqueous paints based on hydro-dilutable alkyd resins, alkyd emulsions, hybrid systems, two-component systems, polyurethane and acrylate dispersions.

The addition compounds of the invention are also mainly suitable for the preparation of solid concentrates such as, for example, pigment concentrates. For this purpose, the compounds of the invention are initially introduced into a vehicle, such as organic solvents, plasticizers and / or water, and the solids to be dispersed are added while stirring. Additionally, these concentrates may include binders and / or other auxiliaries. With the addition compounds of the invention, however, it is mainly possible to prepare pigment, pigment free and stable concentrates. It is also possible to use the compounds of the invention to prepare fluid solids concentrates from compressed pigment cakes. In this case, the compound of the invention is mixed with the compressed cake which may additionally contain organic solvents, plasticizers and / or water, and the resulting mixture is dispersed. Prepared in their different ways, solids concentrates can then be incorporated into different substrates such as, for example, alkyd resins, polystyrene resins, acrylate resins, polyurethane resins or epoxy resins. However, the pigments can also be dispersed directly in the addition compounds of the invention, without solvent, and are particularly suitable for pigmenting thermoplastic and duroplastic polymer formulations.

The addition compounds of the invention can also be used advantageously in the manufacture of color filters for liquid crystal indicators, liquid crystal displays, color resolution devices, sensors, plasma screens, SED-based indicators (Surface conduction Electron emitter Display or Screen with conductive surface emitting electrons) and for MLCC (Multi Layer Ceramic Compounds or multilayer ceramic compounds). MLCC technology is used in the production of micro chips and printed circuit boards.

The addition compounds of the invention can also be used to produce cosmetic preparations such as, for example, makeup, powders, lipsticks, hair paints, creams, nail varnishes and sunscreen products. These may be present in the usual forms such as, for example, water / oil or oil / water emulsions, solutions, gels, creams, lotions or sprays. The addition compounds of the invention can be used advantageously in dispersions that are used to produce these preparations. These dispersions may contain vehicles that are normal for these purposes in cosmetology such as, for example, water, castor oil or silicone oils and solids such as organic and inorganic pigments, such as titanium dioxide or iron oxides, for example. .

In addition, the use of an addition compound of the invention to produce a pigmented paint which in particular serves to produce a pigmented coating on a substrate, in which case the pigmented paint is applied to a substrate and the paint is also object of the invention. pigmented that has been applied to the substrate is baked

or is cured and / or reticulated.

Dispersants can be used alone or in conjunction with customary binders of the prior art. When used in polyolefins, for example, it may be advantageous to use corresponding olefins of low molecular weight as support materials, together with the dispersant.

A use according to the invention of the addition compounds also consists in the preparation of solids in the form of dust particles and / or fiber particles, capable of dispersing, mainly pigments or dispersible plastic fillers, in which case the particles are coated with the addition compound of the invention. Coatings of this type of organic as well as inorganic solid substances are carried out in a known manner as described in EP-A-0 270 126, for example. In this case, the solvent or emulsifier can be removed or remain in the mixture with the formation of pastes. These pastes are common commercial products and may additionally include binder fractions and also other auxiliaries and additives. Specifically in the case of pigments, it is possible that the pigment surface is coated during or after the synthesis of the pigments by adding, for example, the products of addition of the invention to the pigment suspension or during or after of pigment finish. The pigments pretreated in this way are distinguished by the ease of incorporation and also by the improved viscosity, flocculation and brightness behavior and by the superior color stability when compared to untreated pigments.

fifteen

25

35

Four. Five

55

E09711814

07-28-2014

In addition to the application described above, as dispersants and / or coating materials for solids in the form of powder and fibers, the addition compounds of the invention can also be used as viscosity reducers and compatibilizers in synthetic resins. An example of such synthetic resins are the so-called "sheet molding compounds" (SMC for sheet molding compounds) and "mass molding compounds" (BMC for bulk molding compounds), which are composed of high-saturated saturated polystyrene resins contents of loading material and fiber. Its production and processing is described, for example, in DE-A-36 43007. A problem in the mixtures of synthetic resins of SMC and BMC is that polystyrene (PS) is often added to the formulation in order to reduce Shrinkage during processing. PS is not compatible with the unsaturated polystyrene resins used and a separation of the components occurs. When mixtures of SMC or BMC filled with PS are being used, the additives of the invention, because of their good dispersion qualities, are capable of causing compatibility between PS and the unsaturated polystyrene resins whereby the stability during storage is increased and the safety of processing such mixtures.

In many cases, for example even in polyol mixtures, incompatible polyol diisocyanate or polyol propellant mixtures, used for the production of polyurethane, by means of the addition compounds of the invention it is possible to totally or partially prevent the separation problems that result of this incompatibility and affect dispersions, especially emulsions.

The addition compounds of the invention are preferably added in an amount of 0.01 to 10% by weight with respect to the total amount of the formulation. With respect to the solid to be dispersed, they are used in an amount preferably from 0.5 to 100% by weight. When solids to be dispersed with difficulty are used, the amount of addition compounds of the invention employed can be absolutely greater. The amount of dispersant generally depends on the surface to be coated with the substance to be dispersed. For example, if titanium dioxide is used as a pigment, the amount of dispersant is lower than in the case of, for example, carbon black. In general terms it can be said that the amount of dispersant necessary to disperse inorganic pigments is less than for organic pigments since the latter have a higher specific surface area and, therefore, a larger dispersant amount is needed. Typical levels of addition for inorganic pigments are 1-10% by weight, for organic pigments 10-30% by weight (respectively expressed as active substance of addition compounds with respect to the pigment). In the case of pigments in the form of very fine particles (for example, some carbon black), amounts of 30-80% by weight or more need even be added.

As a criterion of sufficient pigment stabilization it is possible, for example, to use color stabilization, brightness and transparency of the pigment dispersion or the degree of flotation (erasure test) in the case of a white mixture.

The dispersion of solids can be carried out as an individual dispersion or as a dispersion mixed with two or more pigments simultaneously, in which case the best results are generally achieved with individual dispersions. When using mixtures of different solids, opposite charges may result on the surface of the solids, which leads in a reinforced manner to agglomerations in the liquid phase. In these cases, it is often possible to use the addition compounds of the invention to achieve an equal sign charge, generally a positive charge for all particles and therefore prevent instabilities due to charge difference. The dispersants achieve their optimum effect when they are added to the ground material, particularly if the solid to be dispersed is mixed only with the additive and optionally with the solvents ("premix"), since in that case the additive is capable of preferentially adsorbing on the surface of the solid without having to compete with the binder polymers. In practice, however, this procedure is necessary only in exceptional cases. If necessary, the addition compounds can also be used below (such as the so-called "post-additives"), for example in order to solve problems of flotation or flocculation in a finished painted pothole. Usually, however, high doses of additive are required in this case.

In some cases the addition compounds of the invention can exert a more or less pronounced influence on the rheology of the system. In such cases, therefore, they can also optionally be used for rheology control in combination with other rheological additives such as fumed silica, phyllosilicates (bentonites), hydrogenated castor oils or additives BYK®-410, BYK®-420 and BYK ®-425 (BYK Chemie GmbH). In these cases, synergistic effects are often observed. In many cases it is also possible to improve the corrosion control properties of the coatings by using the addition compounds of the invention.

Examples of solids in powder or fiber form are those that can be coated with dispersants, especially organic and inorganic pigments that are used in paints, coating materials, molding compositions or other plastics, and organic or inorganic fillers that are used to fill or reinforce paints, coating materials, molding compositions or other plastics. A

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

E09711814

07-28-2014

Subgroup of such fillers are organic and / or inorganic fibers that are also used as fillers or reinforcing materials.

Examples of pigments that are mono-, di-, tri-and polyazoic pigments, oxazine pigments, dioxazine pigments, thiazine pigments, diketo-pyrrolo-pyrroles, phthalocyanine, ultramarine and other metal complex pigments, indigoid pigments, pigments of diphenylmethane, triarylmethane, xanthene, acridine, quinacridone and methine, anthraquinone, pyrantrone, perylene and other polycyclic carbonyl pigments, inorganic pigments based on carbon black, graphite, zinc, titanium dioxide, zinc oxide, zinc sulphide, zinc phosphate, barium sulfate, lithophones, iron oxide, ultramarine, manganese phosphate, cobalt aluminate, cobalt stannate, cobalt cincate, antimony oxide, antimony sulphide, chromium oxide, chromate zinc, mixed metal oxides based on nickel, bismuth, vanadium, molybdenum, cadmium, titanium, zinc, manganese, cobalt, iron, chromium, antimony, magnesium, aluminum (for example nickel yellow titanium, a bismuth ganadato molybdate or yellow chrome titanium), magnetic pigments based on pure iron, iron oxides and chromium oxide or mixed oxides, metallic pigments comprising aluminum, zinc, copper or bronze as well as perlifying pigments and center lighting pigments fluorescent and phosphorescent. All previously mentioned pigments may be in surface modified form and may have basic, acidic groups.

or neutral on the surface. Acid neutral or modified pigments are preferred, such as oxidized carbon blacks

Other examples are organic or inorganic nano-scale solids having particle sizes below 100 nm, such as certain degrees of carbon black, or particles composed of a metal or semi-metal oxide or hydroxide, and also composite particles. of mixed metal and / or semimetal oxides and / or hydroxides. As an example, it is possible to use the oxides and / or oxyhydroxides of aluminum, silicon, zinc, titanium, etc. in order to prepare solids of this type divided extremely thinly. These oxide, hydroxide or oxide hydroxide particles can be prepared by any of a wide variety of methods such as, for example, ion exchange operations, plasma operations, sol-gel processes, precipitation, crushing (by grinding, for example) or flame hydrolysis, and the like.

Examples of fillers in powder or fiber form are, for example, those composed of powdered particles or fiber of aluminum oxide, aluminum hydroxide, silicon dioxide, diatomaceous earth, silica, quartz, silica gel, talc , kaolin, mica, perlite, feldspar, shale flour, calcium sulfate, barium sulfate, calcium carbonate, calcite, dolomite, glass or coal. Other examples of pigments or fillers are found, for example, in EP-A-0 270 126. Fire retardants such as, for example, aluminum hydroxide or magnesium hydroxide and grinding agents can also be dispersed and stabilized in an outstanding manner. like, for example, silicas.

In the following, the present invention is further illustrated by the following examples.

EXAMPLES

In the case of substances without molecular uniformity, the molecular weights declared - hereinafter as in the preceding description - represent average values of the numerical average. The molecular weights or the average molecular weights in number Mn are determined when hydroxyl or amino groups that can be titrated are present, by determining the end group by determining the OH number or amine number, respectively. In the case of compounds to which an end group determination cannot be applied, the number average molecular weight is determined by gel permeation chromatography versus a polystyrene standard.

As long as something different is not expressed, parts are parts by weight and percentages are percentages by weight.

The free NCO content of the polyisocyanates used and also the course of the reaction of the NCO additions are determined in accordance with EN ISO 9369 by reaction with butylamine and subsequent titration of the excess amine. These methods are also described in Saul Patai "The Chemistry of Cyanates and their Thio Derivates" (Part 1, Chapter 5, 1977).

The preparation of hydroxy functional caprolactone polyesters is carried out as described in EP 158678, for example.

Preparation Examples

Example 1 (comparative example, not inventive)

28.1 parts of polyisocyanate P1 are homogenized with 38.5 parts of BCPE1100 and 22.7 parts of PMA (methoxypropyl acetate). Under inert gas, it is heated to 80 ° C and 0.003 parts of DBTL (dibutyltin dilaurate) are added.

10

fifteen

twenty

25

30

35

40

Four. Five

E09711814

07-28-2014

Stir approximately 1 hour at this temperature until 65% of the NCO groups used have reacted. Then 2 parts of DMAPA are added and stirring is continued at 80 ° C until all the NCO groups have reacted. The product is of medium viscosity and has a solids content of 60% and a diamine number of 12 mg KOH / g. After a few days at 20 ° C the product shows a strong formation of crystals.

The product is not soluble in test benzine, free of aromatics.

Example 2

Similarly to example 1, 38.5 parts of BPO1100 are used instead of BCPE1100. The solids content is 60% and the amine number is 12 mg KOH / g. During storage the product remains homogeneous and liquid. Even during prolonged storage below 0 ° C there is no crystal formation.

In test benzine, free of aromatics, a 10% clear solution can be prepared.

Example 3

Similarly to Example 2, instead of DMAPA, 1.7 parts of DMEA are used. The solids content is 60% and the amine number is 12 mg KOH / g.

Example 4

Similarly to example 2, instead of DMAPA, 2.5 parts of API are used. The solids content is 60% and the amine number is 12 mg KOH / g.

Example 5

Similarly to Example 2, instead of DMAPA, 2.3 parts of DEEA are used. The solids content is 60% and the amine number is 12 mg KOH / g.

Example 6

15.7 parts of polyisocyanate P1 are homogenized with 9.9 parts of BPO1100 and 46.9 parts of PMA. It is heated under a protective gas at 60 ° C and 0.001 parts of DBTL are added. After about an hour, 30% of the used NCO groups have reacted. Then 1.3 parts of a PEG400 are added. At 60 ° C it continues to stir until another 21% of the NCO groups used have reacted. Then 1.9 parts of API are added as well as 24.5 parts of N-methylpyrrolidone and continue to stir at 80 ° C until the remaining NCO groups have reacted. The product has an amine number of 8 mg KOH / g and a solids content of 23%.

Example 7

15.7 parts of polyisocyanate P1 are homogenized with 9.9 parts of BPO1100 and 46.9 parts of PMA. It is heated under protective gas at 60 ° C and 0.001 parts of DBTL are added. After approximately one hour, 30% of the NCO groups employed have reacted. Then 3.15 parts of a PEG1000 are added. At 60 ° C it continues to stir until another 21% of the NCO groups used have reacted. Then 1.9 parts of API are added as well as 24.5 parts of N-methylpyrrolidone and continue to stir at 80 ° C until the remaining NCO groups react completely. The product has an amine number of 8 mg KOH / g and a solids content of 23%.

Example 8

24 parts of polyisocyanate P1 are homogenized with 25.6 parts of BPO1400 as well as 26 parts of PMA and 41.3 parts of ethyl acetate. It is heated under protective gas at 65 ° C and 0.002 parts of DBTL are added. After one hour, 40% of the NCO groups used have reacted. Then 1.5 parts of PEG600 are added. At 65 ° C it continues to stir until another 11% of the NCO groups used have reacted. They are then mixed with 2.3 parts of DMAPA and stirred at 70 ° C, until the remaining NCO groups have reacted. The product is of low viscosity, has a solids content of 35% and amine number of 10 mg KOH / g.

Example 9

To 29.6 parts of polyisocyanate P1, 25.2 parts of ethyl acetate and 0.001 parts of DBTL at 80 ° C are mixed by dropwise adding, slowly, 24 parts of BPO700. After they have reacted 60%

5

10

fifteen

twenty

25

30

35

40

E09711814

07-28-2014

Of the NCO groups used, 2.7 parts of DMEA are added. After the remaining NCO groups have reacted, it is diluted with 17.4 parts of the dipropylene glycol monomethyl ether (PM). The product is of medium viscosity, has a solids content of 43% and an amine number of 11 mg KOH / g.

Example 10

To 37.6 parts of polyisocyanate P1, 50 parts of PMA and 0.001 parts of DBTL at 80 ° C for one hour 37.2 parts of BPO1100 are slowly added dropwise. After 60% of the used NCO groups have reacted, 2.3 parts of DMAPA are added. After the remaining NCO groups have reacted, it is diluted with 17.4 parts of tripropylene glycol monomethyl ether (TPM). The product is of medium viscosity, has a solids content of 40% and an amine number of 9 mg KOH / g.

Example 11

To 29.6 parts of polyisocyanate P1, 65.3 parts of PMA and 0.001 parts of DBTL are slowly added dropwise, for one hour, at 80 ° C, 47.4 parts of BPO1400. After 60% of the used NCO groups have reacted, 2.3 parts of DMAPA are added. After the remaining NCO groups have reacted, it is diluted with 17.4 parts of dipropylene glycol monomethyl ether (DPM). The product is of medium viscosity, has a solids content of 40% and an amine number of 8 mg KOH / g.

Example 12

To 29.6 parts of P3 polyisocyanate, 80.4 parts of PMA and 0.001 parts of DBTL drops are added slowly, for one hour, at 80 ° C, 57.5 parts of BPO1700. After 60% of the used NCO groups have reacted, 2.3 parts of DMAPA are added. After the remaining NCO groups have reacted, it is diluted with 17.4 parts of dipropylene glycol monomethyl ether (DPM). The product is of medium viscosity, has a solids content of 40% and an amine number of 7 mg KOH / g.

Example 13

To 14.4 parts of polyisocyanate P2, 37 parts of PMA and 0.003 parts of DBTL for four hours are slowly added dropwise, at 80 ° C, 41 parts of BPO1100. After 50% of the used NCO groups have reacted, 4.7 parts of API are added. After the remaining NCO groups have reacted, it is diluted with 3 parts of dipropylene glycol monomethyl ether (DPM). The product is of medium viscosity, has a solids content of 60% and an amine number of 21 mg KOH / g.

Legends:

P1 = aromatic TDI polyisocyanurate with a free NCO content of 8.0% as a 51% solution in butyl acetate, for example Desmodur ®IL, Bayer AG

P2 = aliphatic polyisocyanate (HDI-trimerized) with an NCO-free content of 21.8%, for example Desmodur ® N3300, Bayer AG

P3 = aromatic TDI polyisocyanurate with an NCO-free content of 8.0%; as a 51% solution in ethyl acetate, for example Desmodur ® IL EA, Bayer AG

BCPE1100 = monohydroxy functional ε-caprolactone polyester prepared starting with butanol, average molecular weight Mn 1100

BPO700,1100,1400 = monohydroxy functional PO polyether prepared starting with butanol, average molecular weight Mn = 700, 1100 or 1400

PEG 400, 600, 1000 = Polyethylene glycol (dihydroxy functional), average molecular weight Mn 400, 600 or 1000

DMEA = N, N-dimethylaminoethanol

API = aminopropylimidazole

DEEA = N, N-diethylaminoethanol

DMAPA = N, N-dimethylaminopropylamine

E09711814

07-28-2014

Examples of use Use in paste systems Pigment paste with special black 4: Laropal A 81 to 65% in PMA 23.50 parts

5 PMA 22.90 parts Addition compound according to the invention 19.60 parts Carbon black, for example special black 4 (Degussa AG) 34.00 parts

100.00 parts + 10% PMA

10 Dispersion: Dispermat CV / 60 min./ 10000 r / min / 40 ° C / 1 mm beads 1: 1 Special black pigment pastes 4, prepared with examples 2, 3 and 4 Evaluation of the viscosity of visual-paste :

Additive: Evaluation:

Example 2 1 15 Example 3 2 Example 4 1

Rating: 1 = low viscosity, 3 = medium viscosity, 5 = pasty

Claims (18)

5 10 fifteen twenty 25 30 35 E09711814 07-28-2014 1. Addition compounds and their salts, characterized in that the addition compounds can be obtained by the reaction of (a) one or more polyisocyanates with at least two isocyanate groups per molecule with (b1) one or more compounds of the formula (Ia) Y-XH (Ia) where XH represents a reactive group against isocyanates and Y represents a polymeric monomer group, non-reactive against isocyanates, without tertiary amino groups, which it comprises one or more aliphatic, cycloaliphatic and / or aromatic groups, where the compound of the general formula (Ia) has an average molecular mass in number Mn less than 20,000 g / mol and where at least 55% molar of the compounds of the formula (Ia) have an average molecular weight in Mn number of 150 to 10,000 g / mol and which represent XH-functionalized poly (alkylene oxides) whose content of oxide units of alkylene with at least three carbon atoms is 40 to 100 molar relative to the total content of alkylene oxide units, with the proviso that 20% to 90% of the isocyanate groups of component (a) react with the compounds of the formula (Ia), (b2) one or more compounds of the formula (Ib) G- (XH) n ( Ib) where XH represents a reactive group against isocyanates and n represents 2 to 4, and G represents an aliphatic, cycloaliphatic and / or aromatic containing at least 2 carbon atoms, without tertiary amino groups, with average molecular weight in maximum Mn number of 3000, in an amount such that 0 to 60% of the isocyanate groups of the polyisocyanate originally used react, with the proviso that by reactions (b1) and (b2) in total, at least 20% and maximum 90% of the isocyanate groups originally used react, (c1) one or more compounds of the general formula (IIa) Z-Q (IIa) where Q represents -NH2, -NHR or OH, where R represents a linear or branched alkyl group with 1 to 18 carbon atoms, and Z represents a basic organic residue with at least one tertiary amino group that does not contain reactive groups against isocyanate, and (c2) optionally one or more compounds of the general formula (IIb) M-Q (IIb) where Q represents -NH2, -NHR or OH, where R represents a linear or branched alkyl group with 1 to 18 carbon atoms, and 5 10 fifteen twenty 25 30 35 40 E09711814 07-28-2014 M represents an organic residue with a maximum average molecular mass of 1000 g / mol with at least one tertiary amino group and at least one hydroxyl group, with the proviso that at least 10% of the isocyanate groups of component (a) react with component (c1).

2.

Addition compounds according to claim 1, wherein Y optionally contains the heteroatoms O, S, Si and / or N and / or the groups of ether, urethane, carbonate, amide, siloxane and / or ester, and optionally hydrogen is substituted by halogen

3.

Addition compounds according to claim 1 or 2, wherein Z has one or more of the following meanings: A) an aliphatic and / or cycloaliphatic group with at least one tertiary amino group or B) a heterocyclic group with at least one nitrogen atom basic ring, which does not contain a hydrogen atom, in which case the heterocyclic group may be linked to group Q by an organic coupling group.

Four.

Addition compounds according to one or more of claims 1 to 3, in which case at least two different compounds of the formula (Ia) are used.

5.

Addition compounds and their salts according to one or more of claims 1 to 4, characterized in that a part of the monofunctional compounds of the formula (Ia) are polyethers, polyesters, monohydroxy functional polyesters and / or aliphatic and / or cycloaliphatic monoalcohols with 2 to 30 carbon atoms, whose hydrogen atoms are partially replaced by halogen and / or aryl residues.

6.

Addition compounds according to one or more of claims 1 to 5, characterized in that as polyfunctional compounds of the formula (Ib), polyethers, polyesters or di-, tri- or tetrahydroxy functional polyethers are used.

7.

Addition compounds according to one or more of claims 1 to 6, characterized in that they do not contain unsaturated groups.

8.

Addition compounds according to one or more of claims 1 to 7, characterized in that the polyisocyanates are products of diisocyanates containing one or more isocyanurate groups, based on hexamethylene diisocyanate, diisophorondiisocyanate and / or toluylenediisocyanate.

9.

Method for producing the addition compounds according to one or more of claims 1 to 8, wherein a reaction of

(a) one or more polyisocyanates with at least two isocyanate groups per molecule with (b1) one or more compounds of the formula (Ia) Y-XH (Ia) where XH represents a reactive group against isocyanates and Y represents a monomeric or non-reactive polymer against isocyanates, without tertiary amino groups, which comprises one or more aliphatic, cycloaliphatic and / or aromatic groups, where the compound of the general formula (Ia) has an average molecular mass in number Mn less than 20,000 g / mol Y where at least 55% molar of the compounds of the formula (Ia) have an average molecular weight in Mn number of 150 to 10,000 g / mol and which represent XH-functionalized poly (alkylene oxides), whose content of oxide units of alkylene with at least three carbon atoms is 40 to 100 molar relative to the total content of alkylene oxide units, with the proviso that 20% to 90% of the isocyanate groups of component (a) react with the compounds of formula (la), 5 10 fifteen twenty 25 30 35 40 E09711814 07-28-2014 (b2) one or more compounds of the formula (Ib) G- (XH) n (Ib) where XH represents a reactive group against isocyanates and n represents 2 to 4, and G represents an aliphatic, cycloaliphatic and / or aromatic group containing at least 2 carbon atoms, without tertiary amino groups, with average molecular weight in maximum Mn number of 3000 g / mol in an amount such that 0 to 60% of the isocyanate groups of the polyisocyanates originally used react, provided that through reactions (b1) and (b2) at least 20% and maximum 90% are converted into total of the isocyanate groups of the polyisocyanates originally used, (c1) one or more compounds of the general formula (IIa) Z-Q (IIa) where Q represents -NH2, -NHR or OH, where R represents a linear or branched alkyl group with 1 to 18 carbon atoms, Y Z represents a basic organic residue with at least one tertiary amino group which does not contain reactive groups against isocyanate, and (c2) optionally one or more compounds of the general formula (IIb) M-Q (IIb) where Q represents -NH2, -NHR or OH, where R represents a linear or branched alkyl group with 1 to 18 carbon atoms, and M represents an organic residue with an average molecular mass in maximum number of 1000 g / mol with at least one tertiary amino group and at least one hydroxyl group, with the proviso that at least 10% of the isocyanate groups of the component react (a ) with component (c1).

10.

Process for producing an addition compound according to claim 9, wherein the component (a) is first reacted with the component (b1) and optionally (b2) and then a reaction with the component (c1) takes place.

eleven.

Process for producing an addition compound according to one of claims 9 or 10, wherein the component

(a) first reacts with compounds of the general formula (la) and then with compounds of the general formula (Ib).

12.

Use of one of the addition compounds of one or more of claims 1 to 8 or produced according to one or more of the processes according to claims 9 to 11, as dispersant, dispersion stabilizers and / or humectant.

13.

Use of one of the addition compounds of one or more of claims 1 to 8 or produced according to one or more of the processes according to claims 9 to 11, in the preparation or processing of paints, printing inks, inks, paints for paper, leather and textile paints, pastes, pigment concentrates, ceramics, cosmetic preparations, molding compositions and / or smelting compositions based on synthetic, semi-synthetic or natural macromolecular substances.

14.

Use of one of the addition compounds of one or more of claims 1 to 8 or produced according to one or more of the processes according to claims 9 to 11, to prepare pigment concentrates, paints, pastes and / or molding compositions which They contain pigments and / or fillers.

fifteen.

Use of one of the addition compounds according to one or more of claims 1 to 8 or produced according to one or more of the processes according to claims 9 to 11, for coating solid substances in the form of dust particles and / or particles fiber

E09711814 07-28-2014

16.

Use of an addition compound according to claim 15, wherein the solid substances in the form of dust particles and / or fiber particles are pigments and / or dispersible fillers.

17.

Use of one of the addition compounds according to one or more of claims 1 to 8 or produced according to one or more of the processes according to claims 9 to 11, for the preparation of a pigmented paint.

18. Use of an addition compound according to one or more of claims 1 to 8 or produced according to one or more of the processes according to claims 9 to 11, for the preparation of a pigmented coating on a substrate, in which case a Pigmented paint is prepared with the addition compound, where the pigmented paint is applied on the substrate where the pigmented paint applied on the substrate is baked or cured or crosslinked. 19. Solid substances in the form of dust particles and / or fiber particles, characterized in that they are coated with an addition compound according to one or more of claims 1 to 8 or produced according to one or more of the processes according to claims 9 to 11. 20. Solid substances in the form of dust particles and / or fiber particles according to claim 19, wherein the solid substances in the form of dust particles and / or fiber particles are pigments and / or fillers.